New sulphur dyestuffs and process of making



Patented Jan. 12, 1932 UNITED STAT ESPAT ENT OFFICE IE'BWIN KRAMER, OF COII OGNE-DEUTZ, LUDWIG ZEH, OF WIESDOBF-ON-THE-RHINEQAND IBERNHARD BOLLWEG, OF LEVERKUSEN-ON-THE-BHINE, GERMANY, ASSIGNORS T GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELA WARE summon nxnsrurrs Aim rnocnss or MAKING N0 Drawing. Application filed August 12, 1929, Serial No. 385,455, and in Germany October 18, 1928.

@The present invention relates to new sulv phur dyestuffs obtainable from the halogen I ide by sulphurization substitution products of dinaphthylene-dioxand to. a process of preparing same. i I

gAccording to the resent invention, valuable sulphur dyestu s are prepared by heating a halogenated dinapthylene-dioxide with sulphur or with an alkali metal polysulphide at an elevated temperature, say about 150- 250 0., for several hours, Otherwise the process may be carried" out by melting the dinaphthylene-dioxide compound with a mixture of sulphur and an alkali metal-sulphide or -polysulphide. If desired, the formation of our new dyestufi's can be efi'ected by heating the starting components in an inerthigh-boiling organicsolvent, such as nitrobenzene, trichlorobenzene and the like,

'trichlorobenzene. A

to an elevated temperature, say 150250 C., for-several hours. From the melt the dyestuff is-separated in the usual manner by dissolving in an aqueous alkali metalsulphide and precipitating the dyestufl' from its solutionby the addition of an acid. The starting' 'dinaphthylene-dioxide compounds used for the" purpose of our invention may be represented by the following general formula:

wherein hal stands for a halogen atom and n stands for one of the numbers one to ten. They are obtainable by halogenating in the usual manner dinapthylene-dioxide withthe calculated amount of halogen or a suitable compound thereof, such as a sulphurylchloride and the like in a suitable highboiling solvent, for example, nitrobenzene or process of preparing the above identified'starting components is described in our copending application Ser. No."385,475, filed August 12, 1929.

dish-brown.

. tions and dye cotton yellow to blac ish-brown shades of excellent fastness properties. The shades vary with the halogen contentof the starting material, and moreover the nature of halogen itself influences the product, bromine substitution products yielding considerably yellower dyestuffs than the correponding chlorine derivatives.

The invention is illustrated by the following examples, without being limited theret0; 1

Example 1., parts by weight of tetrachlorodinaphthylenedioxide are heated with 15 parts by weight of sulphur for 3 hours at 180-215? C. The melt is ground up and then dissolved with 150 parts by weight of crystallized sodium sulphate at 120-130 C. and separated in the customary manner. The dyestuff. forms a dark powder, which dissolves in water with sodium sulphide with ared coloration and dyes cotton the same shades, which after hanging yields a red Asimilar dyestuif is obtained by carrying out the heating with sulphur in Ewample 2-15 parts by weight of dichlorodinaphthylenedioxide are heated with 120 parts by weight of crystallized sodium sulphide and 48 parts by weight of sulphur for 7 hours at 180-200 C. The dyestufi is purified by dissolving with sodium sulphide, filtering and precipitating with acid. It is a brownish-yellow powder, dissolves with sodium sulphide with a yellow coloration and dyes cotton after hanging a yellowish brown, fast to boiling.

By using in this example trichlorodinaphthylenedioxide a reddish yellow brown dye stuff is obtained.

Ewample 3.22.-5 parts by weight of tetrachlorodinaphthylenedioxide are heated with 180 parts by weight of crystallized sodium sulphide and 96 parts by weight of sulphur for 7 hours at 180200 C. The dyestuflf is purified by dissolving the melt in water with 180 parts by weight of crystallized sodium 65 G. for several hours.

sulphide, filtering and precipitating with acid. It is a reddish-brown powder, which dissolves in water with sodium sulphide with a red coloration, dyes cotton the same shade and after hanging yields a brownish-red of light. V V I Example 4-15 parts by weight of pen tachlorodinaphthylene-dioxide are heated sulphur for 7 hours at 180-200 V C. and worked up as described in Example Thus is obtained-a violet-brown powder, which dissolves in water with sodium sulphide with a red coloration and-after hanging yields clear, .very fast, reddish-brown dyeings on cotton.

Example 5.2 5 parts by weight of tetrabromodinaphthylene-dioxide are heated with 120 parts by weight of sodium sulphide and 56parts by weight of sulphur to 180-230 C.

in'the course of 12 hours. purified by disolving with sodium sulphide and precipitating with acid. It is a yellowish-brown powder, which dissolves in water with sodium sulphide with an orange-yellow coloration and yields on cotton a yellowishbrown, fast to boiling and light. 1 h Ewamle6.25 parts by weight of hexachlorodinaphthylene-dioxide are heated with -180parts by weight of crystallized sodium sulphide and 96 parts by weight of sulphur for 7 hours.at'180200 C. and worked up as described in Example 5. The dyestuff forms a dark brown powder, which dyes cotton blackish-brown from a sodium sulphide bath, exhibiting a red coloration. 1

{On replacing the hexachloro derivative by Idecachlorodinaphthylene-dioxide and heat:

ing for '12 hours at 180-230 C. a gray dyeing sulphur dyestuif is'obtained.

- By the term sulphu'rating agent we mean sulphur, alkali metal polysulphides and mixtures of sulphur with an alkali metal-sulphide or poly-sulphide.

' We'claim:

g 1. The process which comprises sulphurating a dinaphthylene-dioxide compound of '50 the general formula:

wherein hal stands for a halogen atom and on for one of the numbers one to ten by heatingthe same with a sulphurating agent at a temperature of about 150 to about 250 very satisfactory fastness to boiling and.

with 120 parts by weight of crystallized sodium sulphide and 60 parts by weight of The dyestuff is excellent fa'stness properties.

2. The process which comprises sulphurating a dinaphthylene-dioxide compound of the general formula:

wherein half-stands for a halogen atom and n stands for one of the numbers one to ten, by heating the same in an'inert high-boiling organic solvent with a sulphurating agent at a temperature'of about 150 to about 250 C. for several hours. i

3. The process which comprises sulphuratin a dinaphthylene-dioxide compound of the b general formula wherein hal stands for a halogen atom and n7? stands for one of the numbers one to ten, said dyestuffs beingigenerally yellow to blackish-brown powders, soluble in aqueous alkali metal sulphide solutions and dyeing cotton yellow to blackish-brown shades of 6. As new products thesulphur dyestufi's obtainable by sulphurating a dina hthylenedioxide compound of the general ormula:

wherein n stands for one of the numbers four and five, said dyestufi's being reddishbrown to Violet-brown powders, soluble in aqueous alkali metal sulphide solutions and dyeing cotton brownish-red shades of excellent fastness properties.

As a new product the sulphur dyestufl obtainable by sulphurating tetrachlorodinaphthylene-dioxide, being a reddish-brown powder, soluble in aqueous alkali metal sulphide solutions and d eing cotton clear reddish-brown shades good fastness properties. I g

In testimony whereof we have hereunto set our hands.

ERWIN KRAMER. [L. s] LUDWIG ZEH. [L. s.] BERNHARD BOLLWEG. [L. 8.] 

